Proteomic analysis of transducin beta-subunit structural heterogeneity

Partially purified transducin was resolved using two-dimensional gel electrophoresis (2-DE). Peptide mass fingerprinting of several different spots believed to correspond to the 37 kDa beta-subunit of transducin (T(beta)) was performed. Spots were excised and proteolyzed using modified trypsin. Matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) was performed on the peptide mixture resulting from each spot. As many as six spots with different pI, ranging from 5.2 to 6.1, were observed when separated using 2-DE. MALDI peptide mass fingerprinting determined with high probability that all of the spots were the same gene product, guanine nucleotide-binding protein G(I)/G(S)/G(T) beta-subunit 1 (GNB1; T(beta1)). This suggested that post-translational modification was responsible for the differences in pI. Phosphorylation experiments showed that at least one T(beta1) spot was phosphorylated in vitro with [gamma-(32)P]ATP by an endogenous kinase. Treatment of T(beta) with alkaline phosphatase caused a large change in the spot pattern of T(beta), suggesting that phosphorylated T(beta) is a substrate for alkaline phosphatase. We conclude that T(beta1) constitutes over 99% of the T(beta) expressed in bovine rod outer segments and displays structural heterogeneity that is due to post-translational modification. We also conclude that some, but not all, of the heterogeneity observed is due to phosphorylation of Tb1.     

Distribution functions of structural heterogeneity of microporous adsorbents

The distribution functions of structural heterogeneity of microporous adsorbents have given. Influences of adsorbents and adsorbates types on this heterogeneity have been studied.

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Verteilungsfunktionen für die Struktur-Heterogenität von mikroporösen Adsorbentien

Zusammenfassung Es werden Verteilungsfunktionen für die strukturelle Heterogenität von mikroporösen Adsorbentien angegeben. Die Einflüsse der Adsorbens- und Adsorbatarten auf diese Heterogenität wurden untersucht.

     

Clickable dendronized copolymers for introducing structural heterogeneity

A new class of shape-persistent dendronized copolymers 1[Gn]4–5(a–d) (n = 1, 2) with an alternating structure was synthesized via a combination of conventional radical copolymerization and Cu(I)-catalyzed click reaction (i.e. CuAAC). Firstly, azide-functionalized dendronized copolymers 1[Gn]4-N₃ that could be used as “clickable” single molecular platforms were synthesized through two steps: (i) the preparation of methanesulfonate-modified copolymers by a radical copolymerization of styrene derivatives pendant with Percec-type polyether dendron and methanesulfonate-containing maleimide; (ii) the replacement reaction of methanesulfonate unit with sodium azide. Then a series of functional molecules bearing an alkyne group, respectively, such as anthracene and mini-dendritic wedges, were attached onto each maleimide unit of the copolymers through CuAAC. Moreover, a postmodification of the denpols bearing anthracene has been conducted using Diels–Alder cycloaddition between the attached anthracenes and the maleimide dendron, demonstrating that more complicated denpols can be fabricated. These novel dendronized copolymers have been characterized by nuclear magnetic resonance spectroscopy, atom force microscopy, Fourier transform infrared spectroscopy, UV–vis spectroscopy.     

Fluorescence correlation spectroscopy evidence for structural heterogeneity in ionic liquids

In this work, we provide new experimental evidence for chain length-dependent self-aggregation in room temperature ionic liquids (RTILs) using fluorescence correlation spectroscopy (FCS). In studying a homologous series of N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide, [C(n)MPy][Tf(2)N] RTILs of varying alkyl chain length (n = 3, 4, 6, 8, and 10), biphasic rhodamine 6G solute diffusion dynamics were observed; both the fast and slow diffusion coefficients decreased with increasing alkyl chain length, with the relative contribution from slower diffusion increasing for longer-chain [C(n)MPy][Tf(2)N]. We propose that the biphasic diffusion dynamics originate from self-aggregation of the nonpolar alkyl chains in the cationic [C(n)MPy](+).     

Consequence of assuming gamma-type distribution for characterizing structural heterogeneity of microporous solids

Extensive model studies were carried out for the gamma-type distribution, which was used to characterize structural heterogeneity of microporous solids. This distribution lead to a simple equation, which gave a good representation of many adsorption isotherms measured on microporous activated carbons. Assuming physically realistic values of the adsorption parameters, the gamma-type distribution curves were calculated together with curves of the adsorption isotherm, micropore distribution, adsorption potential distribution, enthalpy and entropy of adsorption.

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Die Konsequenz der Annahme einer Gamma-Typ-Verteilung bei der Charakterisierung der strukturellen Heterogenität von mikroporösen Feststoffen

Zusammenfassung Es wurden für die Gamma-Typ-Verteilung, die zur Charakterisierung der strukturellen Heterogenität von mikroporösen Feststoffen genutzt wurde, ausgedchnte Modellrechnungen durchgeführt. Diese Verteilung führte zu einer einfachen Gleichung, die eine gute Darstellung vieler Adsorptionsisothermen an mikroporös-aktiviertem Kohlenstoff erlaubt. Unter der Annahme von physikalisch realistischen Werten für die Adsorptionsparameter wurden die Gamma-Typ-Verteilungskurven zusammen mit Kurven für die Adsorptionsisothermen, der Mikroporenverteilung, der Adsorptionspotentialverteilung und der Enthalphie und Entropie der Adsorption berechnet.

     

Esterification with orthophosphoric acid of cellulose samples with different extents of structural heterogeneity

Modification of cellulose samples with different extents of structural heterogeneity by esterification with orthophosphoric acid in the temperature range 140?C160??C was studied. The reaction yielded cellulose phosphates containing 3.2?C6.0 wt % P, with the ion-exchange capacity of 2.2?C3.0 mg-equiv g^?1. Introduction of phosphorus into cellulose leads to a slight decrease in the structural heterogeneity. The polymer with the lower ordering index is characterized by the higher phosphorus content, which suggests that the reaction mainly occurs in the amorphous part of the polymer.     

Critical Crystal-Chemical Parameters Controlling T c of HTSC Cuprates

For all high-temperature superconductive (HTSC) cuprate phases, an empirical relationship has been found between the temperature of the transition to the superconducting state (T _c) and the ratio between the interatomic distances of copper atoms along the diagonal of the CuO₂ plane and the sum of effective distances from the CuO₂ plane to two adjacent cation planes calculated with regard to the charge and size of the cations and doping atoms. The critical parameters controlling T _c are discussed.     

Importance of structural and chemical heterogeneity of activated carbon surfaces for adsorption of dibenzothiophene

The performance of various activated carbons obtained from different carbon precursors (i.e., plastic waste, coal, and wood) as adsorbents for the desulfurization of liquid hydrocarbon fuels was evaluated. To increase surface heterogeneity, the carbon surface was modified by oxidation with ammonium persulfate. The results showed the importance of activated carbon pore sizes and surface chemistry for the adsorption of dibenzothiophene (DBT) from liquid phase. Adsorption of DBT on activated carbons is governed by two types of contributions: physical and chemical interactions. The former include dispersive interactions in the microporous network of the carbons. While the volume of micropores governs the amount physisorbed, mesopores control the kinetics of the process. On the other hand, introduction of surface functional groups enhances the performance of the activated carbons as a result of specific interactions between the acidic centers of the carbon and the basic structure of DBT molecule as well as sulfur-sulfur interactions.     

Structural and thermal properties of the HTSC Hg-1201

The lattice parameters of Hg_xBa₂O₄₊ were determined by X-ray powder diffraction as a function of temperature from 10 to 310 K. The fitting of the parameters yielded the thermal expansion coefficients of the superconducting oxide and demonstrated the anisotropy characteristics of the polycrystalline material. The effect of the irreversible loss of Hg on the lattice parameters is reported.This work was supported in part by the Italian Consiglio Nazionale delle Ricerche.     

Field evaporation and field desorption from HTSC single-crystal surfaces

The problems of field evaporation (FE) and field desorption (FD) from surface of oxide high-temperature superconductors (HTSC) of 123, 2212 and 2223 type are discussed. Wide-angle atom probe, usual time-of-flight atom probe and field ionization magnet mass-spectrometer have been used in these experiments. The main purpose of the investigation was to search for effects connected with phase transition. Therefore, the experiments were carried out over a wide range of temperatures: from T of solid nitrogen to room T.

Composition of pure, contaminated and deep corroded surface and typical species of FE and FD spectra have been studied. The bond energies between some atoms (or clusters) and the surface have been estimated on the basis of experimental results and FE theory. From these estimations, and from discovering of correlated ion pairs, it was concluded that the redistribution of local bonds should be taken into consideration in this case. The increase of FE rate was observed at cryogenic temperatures. Various versions are discussed to explain these effects. Some of them are connected with phase transition.

A detailed study of FD of water protonized clusters is performed and the catalytic activity of HTSC crystal surfaces is discussed.     

Sub-Tc electron transfer at the HTSC/polymer interface

The first kinetic measurements for electron transfer (ferrocene/ferricinium reaction) at the interface between an HTSC (Tl,Pb1223) and a redox polymer (ferrocene-tagged poly-pyrrole) show that superconductivity affects electron transfer rate, which thus offers a novel probe of the superconducting state.     

Effect of structural heterogeneity of ethylene-vinylacetate copolymers modified by ethyl silicate on their stress-strain characteristics

Structural and morphological studies of ethylene-vinylacetate copolymers modified by tetraethoxysilane have been performed. It has been found that microheterogeneity of cevilens is caused by phase separation of oligomeric siloxane fragments. The observed effect of elastication in CEVA-ETS systems is due to the structural heterogeneity of the material.     

New symmetric azomethinic dimer: the influence of structural heterogeneity on the liquid crystalline behaviour

The paper deals with the study of the thermotropic liquid crystalline properties of a new azomethinic symmetric dimer and some of its structural heterogeneous mixtures with one of its reagents. Their thermotropic behaviour was monitored by polarised light microscopy, differential scanning microscopy and variable temperature X-ray diffraction measurements. The influence of the structural heterogeneity on the mesomorphic behaviour was established and some similarities with the mesomorphic behaviour of the polydisperse polymers were underlined.     

Topics on the preparation of HTSC via solid state reaction and melting process

The problems of the preparation of High Temperature Superconductors by sintering and melting are examined. Results of the thermal properties of the total substitution of Yttrium by a rare earth element are reported. The process of fabrication of HTSC after high temperature decomposition is indicated. The results of first characterisation are also reported.

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Zusammenfassung Probleme der Herstellung von Hochtemperatur-Supraleitern durch Sinter- und SchmelzvorgÄnge wurden untersucht.Es werden Resultate der thermischen Auswirkungen der vollstÄndigen Substitution von Yttrium durch Seltenerdelemente wiedergegeben. Der Prozess einer Herstellung von HT-Supraleitern nach thermischer Zersetzung im Bereich hoher Temperatur wird beschrieben, und es werden Resultate erster Charakterisierungen mitgeteilt.

     

IR linewidth and intensity amplifications of nitrile vibrations report nuclear-electronic couplings and associated structural heterogeneity in radical anions

Conjugated molecular chains have the potential to act as “molecular wires” that can be employed in a variety of technologies, including catalysis, molecular electronics, and quantum information technologies. Their successful application relies on a detailed understanding of the factors governing the electronic energy landscape and the dynamics of electrons in such molecules. We can gain insights into the energetics and dynamics of charges in conjugated molecules using time-resolved infrared (TRIR) detection combined with pulse radiolysis. Nitrile ν(C N) bands can act as IR probes for charges, based on IR frequency shifts, because of their exquisite sensitivity to the degree of electron delocalization and induced electric field. Here, we show that the IR intensity and linewidth can also provide unique and complementary information on the nature of charges. Quantifications of IR intensity and linewidth in a series of nitrile-functionalized oligophenylenes reveal that the C N vibration is coupled to the nuclear and electronic structural changes, which become more prominent when an excess charge is present. We synthesized a new series of ladder-type oligophenylenes that possess planar aromatic structures, as revealed by X-ray crystallography. Using these, we demonstrate that C N vibrations can report charge fluctuations associated with nuclear movements, namely those driven by motions of flexible dihedral angles. This happens only when a charge has room to fluctuate in space.

Quantification of the intensity and linewidth of the ν(C N) IR band in a series of neutral and anionic nitrile-functionalized oligophenylenes reveals that the C N vibration is coupled to nuclear and electronic structural changes.     

Effect of the length of the cation substituent on the scale of structural heterogeneity in ionic liquids with low-molecular additions

The structural properties of ionic liquid-low-molecular substance binary mixtures were studied using the integral equation theory. Main attention was paid to the dependence of the characteristic scale of the structural inhomogeneities of a mixture on the length of the cation tail at different concentrations of the low-molecular addition. The typical morphology of pure ionic liquid is preserved in a mixture, the low-molecular admixture leading to a set of the characteristic scales of ordering of the mixture components in the nanometer range.     

Study of structural and dynamic properties of liquid phenyltrimethoxysilane

Herein, we present a combined experimental and computational study of liquid phenyltrimethoxysilane. A femtosecond time-resolved optical Kerr effect experiment has been performed to study the rotational diffusion of the molecule. A new all-atoms molecular model of the compound, based on the OPLS force field, has been developed to reproduce the rotational diffusion time constant and other physical and dynamic properties available in the literature. The density obtained from the simulations is 1074 ± 4 kg m(-3), which is within 1% of the experimental value of 1062 kg m(-3). The viscosity from the simulations is 1.6 ± 0.1 mPa s while the experimental value is 2.1 mPa s. The average bulk dipole moment of 1.8 ± 0.5 Debye obtained from the simulation matches the experimental value of 1.77 Debye. The average relative dielectric constant from the simulations is 3.86 ± 0.04, which is within 13% of the experimental value (4.4). The rotational diffusion time of the dipole moment obtained from the simulations is 20.39 ± 0.06 ps, which is in excellent agreement with the experimental value of 20 ± 1 ps obtained from our measurements. The new model has also been used to calculate structural and dynamic properties of the molecule not yet determined experimentally.